201112466 六、發明說明： 【發明所屬之技術領域】 本發明實施例大致係關於鋰離子電池，更明確地係 關於利用薄膜沉積處理製造上述電池之方法。 ” 【先前技術】 充電快速、高容量的能量儲存裝置（諸如，超級電容與 鋰（Li)離子電池）係用於數目漸增之應用中，包括可攜式 電子產品、醫療裝置、運輸工具、併網型大能量儲存器、 可替換能量儲存器及不間斷電源（ups)。現代可充電能量 儲存裝置中，集電器係由導電體所製成。正集電器（陰極） 之材料實例包括、不鏽鋼與錄。負集電器（陽極）之材 料實例包括銅（Cu)、不鏽鋼與鎳（Ni)。上述集電器形狀可 為落、臈或薄S，其之厚度通常在約6纟5〇陣之間。 一般的鋰離子電池係由電解液或固體聚合物電解質所 刀隔之碳陽極與鋰金屬氧化物或磷酸鹽陰極所組成，電 解液係由有機溶劑（例如，碳酸乙烯酯）中之鋰鹽（諸如， PFs L1BF4或UCIO4)所組成，而固體聚合物電解質（例 如，聚氧化乙烯）與鋰鹽錯合與/或由液態電解質所填 充。陰極材料通常選自鋰過渡金屬氧化物，諸如 LiMn2〇4、LlC〇〇2、LiNi〇2、或犯、u、Mn 與 c〇 氧化 2、、且〇 ’且包括導電微粒（諸如，碳或石墨）及接合物 料陰極材料被視為鋰-嵌合化合物，其中導電材料數 201112466 量範圍在約〇_1%至約15%重量百分比。可將陰極材料以 糊狀物並在熱滾輪間擠壓’或噴塗成溶液或漿狀物而施 力至導電板電極’並將得到之基板乾燥以移除液態載體。 ^常將石墨用來作為陽極材料，且其之外形為链彼合 中-碳微粒（MCMB)粉末，由直徑約1〇㈣之⑽廳所 構成。將鋰-嵌合MCMB粉末散佈於聚合接合物基質中。 接合物基質之聚合物係由熱塑性聚合物（包括具有橡膠 彈性之聚合物）所構成《聚合接合物用以將mcmb材料 粉末結合在一起以排除破裂形成並避免集電器表面上 MCMB粉末之碎裂。聚合接合物數量範圍在約2%至約 30%重量百分比之間。可用糊狀物並在熱滾輪間擠壓， 或用液態溶液施加聚合物/MCMB混合物，並將得到之基 板乾燥以移除溶劑。 某些Li-離子電池利用分隔板，其係由微孔聚烯烴聚合 物（例如’聚乙缔泡棉）所製成，並在一不同製造步驟中 應用。分隔板通常填充滿上述之液態電解質以構成完成 體電池。 隨者薄膜Li -離子電池應用持續成長，丞需較小、較輕 且可更具成本效益地製造之薄膜Li-離子電池。 【發明内容】 本文所述實施例提供在基板上形成層之方法，其藉 由：提供第一前驅物至處理腔室、耦接能量至第一前驅 5 201112466 物中以形成經活化之前驅物、引導經活化之前驅物朝向 基板、混合經活化之前驅物與第二前驅物以形成沉積混 合物、並在基板上沉積包括由經活化之前驅物所形成之 奈米晶體的層。 其他實施例提供在基板上形成電化學薄膜的設備，設 備具有封圍基板支撐件與分配器之處理腔室，分配器包 括活化腔室，流體連通於前驅物源；電功率源，耦接至 活化腔室，混合區，流體連通於活化腔室，混合區具有 指向基板支撐件之出口；及第一管道，具有配置於基板 支撐件附近且與混合區有所間隔之開口。 其他實施例提供在基板之導電表面上形成電化學薄膜 的a又備，设備具有持續移動的基板輸送器及配置於基板 輸送器上之分配器，分配器包括具有複數個喷嘴之活化 腔至，3玄些噴嘴朝向基板輸送器延伸並指向與基板輸送 器移動方向垂直之方向，活化腔室流體連通於一或多個 電化學前驅物源；電功率源，耦接至活化腔室；環狀管 道，圍繞各個噴嘴配置，以攜帶可燃氣體混合物至各個 喷嘴末端處之混合區域；及複數個頭，配置於基板輸送 器附近並與複數個喷嘴有所間隔，各個頭自管道延伸以 分配第二前驅物。 其他實施例提供在基板上形成層的方法，其藉由：提 供電化學沉積材料的漿狀物至處理腔室；提供包括過量 碳的可燃氣體至處理腔室；形成電化學沉積材料的奈米 晶體；及在基板上沉積奈米晶體。 201112466 其他實施例提供在基板上形成電化學層的方法，其藉 由：形成包括電化學前驅物之漿狀物，電化學前驅物包 括經；在惰氣中霧化前驅物混合物；將霧化之前驅物與 包括過量碳的可燃氣體混合物流入處理腔室；讓可燃氣 體混合物反應以形成電化學前驅物的奈米晶體，奈米晶 體上塗覆有含碳塗層；使處於一流（stream)中的奈米晶體 離開處理腔室並朝向基板流動；添加聚合物接合物至流 以形成沉積混合物；及在基板上沉積該沉積混合物。 其他貫施例提供在基板上形成電化學薄膜的設備，設 備具有封圍基板支撐件與分配器之處理腔室分配器具 有乾燥腔室，流體連通於前驅物源與可燃混合物源；點 火源，耦接至乾燥腔室；及接合物喷塗埠，配置於基板 支撐件附近且與分配器有所間隔。 其他實施例提供在基板導電表面上形成電化學薄膜的 '備D又備具有持續移動的基板輸送器及配置於基板輸 ' 器为配器包括具有複數個喷嘴之奈米晶 體形成腔室，該此崦邊知太# > μ 二嘴嘴朝向基板輸送器延伸並指向與基 板輸送器移動 •、 向垂直之方向，奈米晶體形成腔室流體 連通於一或多個雷化與a 电化于别驅物源；可燃氣體源，耦接至 奈米晶體形成腔官.β 至，及複數個頭，配置於基板輸送器附BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates generally to a lithium ion battery, and more particularly to a method for manufacturing the above battery by a thin film deposition process. [Prior Art] Fast-charging, high-capacity energy storage devices such as supercapacitors and lithium (Li) ion batteries are used in a growing number of applications, including portable electronics, medical devices, transportation vehicles, Grid-connected large energy storage, replaceable energy storage and uninterruptible power supply (ups). In modern rechargeable energy storage devices, collectors are made of electrical conductors. Examples of materials for positive collectors (cathodes) include Examples of materials for the negative collector (anode) include copper (Cu), stainless steel, and nickel (Ni). The above current collectors may be in the form of a drop, a 臈 or a thin S, and the thickness thereof is usually about 6 纟 5 〇 A general lithium ion battery is composed of a carbon anode separated by an electrolyte or a solid polymer electrolyte and a lithium metal oxide or a phosphate cathode, and the electrolyte is made of an organic solvent (for example, ethylene carbonate). A lithium salt (such as PFs L1BF4 or UCIO4) is composed, and a solid polymer electrolyte (for example, polyethylene oxide) is mixed with and/or filled with a lithium salt. The cathode material is usually From lithium transition metal oxides, such as LiMn2〇4, L1C〇〇2, LiNi〇2, or ruins, u, Mn and c〇 oxidize 2, and 〇' and include conductive particles (such as carbon or graphite) and bonding The material cathode material is considered to be a lithium-chimeric compound, wherein the amount of conductive material 201112466 ranges from about 〇_1% to about 15% by weight. The cathode material can be extruded as a paste and between hot rollers. Applying a solution or slurry to the conductive plate electrode 'and drying the resulting substrate to remove the liquid carrier. ^ Graphite is often used as the anode material, and the outside is formed as a chain-carbon particle (MCMB) a powder consisting of a chamber having a diameter of about 1 〇 (4). The lithium-chimeric MCMB powder is dispersed in a polymeric conjugate matrix. The polymer of the conjugate matrix is composed of a thermoplastic polymer (including a polymer having rubber elasticity). The polymeric conjugate is constructed to bond the mcmb material powders together to eliminate crack formation and to avoid chipping of the MCMB powder on the surface of the current collector. The amount of polymeric conjugate ranges from about 2% to about 30% by weight. Paste Squeeze between hot rolls, or apply a polymer/MCMB mixture with a liquid solution, and dry the resulting substrate to remove the solvent. Some Li-ion batteries utilize a separator plate that is made of a microporous polyolefin polymer ( For example, 'polyethylene foam" is used in a different manufacturing step. The separator is usually filled with the above liquid electrolyte to form a finished battery. The application of the thin film Li-ion battery continues to grow. Small, lighter, and more cost-effectively fabricated thin film Li-ion battery. SUMMARY OF THE INVENTION Embodiments described herein provide a method of forming a layer on a substrate by providing a first precursor to a processing chamber a chamber, coupling energy to the first precursor 5 201112466 to form an activated precursor, directing the activated precursor toward the substrate, mixing the activated precursor and the second precursor to form a deposition mixture, and forming a deposition mixture on the substrate The deposition includes a layer of nanocrystals formed by the activated precursor. Other embodiments provide an apparatus for forming an electrochemical film on a substrate having a processing chamber enclosing a substrate support and a dispenser, the dispenser including an activation chamber in fluid communication with the precursor source; an electrical power source coupled to the activation a chamber, a mixing zone, in fluid communication with the activation chamber, the mixing zone having an outlet directed toward the substrate support; and a first conduit having an opening disposed adjacent the substrate support and spaced from the mixing zone. Other embodiments provide a substrate for forming an electrochemical film on a conductive surface of a substrate, the device having a substrate transporter that continuously moves and a dispenser disposed on the substrate conveyor, the dispenser including an activation chamber having a plurality of nozzles to 3, some of the nozzles extend toward the substrate conveyor and point in a direction perpendicular to the direction of movement of the substrate conveyor, the activation chamber is in fluid communication with one or more electrochemical precursor sources; the electrical power source is coupled to the activation chamber; a conduit disposed around each nozzle to carry a combustible gas mixture to a mixing region at the end of each nozzle; and a plurality of heads disposed adjacent the substrate conveyor and spaced apart from the plurality of nozzles, each head extending from the conduit to dispense a second precursor Things. Other embodiments provide a method of forming a layer on a substrate by: providing a slurry of electrochemically deposited material to a processing chamber; providing a combustible gas comprising excess carbon to the processing chamber; forming a nanoparticle of electrochemically deposited material Crystal; and depositing nanocrystals on the substrate. 201112466 Other embodiments provide a method of forming an electrochemical layer on a substrate by: forming a slurry comprising an electrochemical precursor, the electrochemical precursor comprising: atomizing the precursor mixture in an inert gas; The precursor is mixed with a combustible gas mixture comprising excess carbon into the processing chamber; the combustible gas mixture is reacted to form a nanocrystal of the electrochemical precursor, the nanocrystal is coated with a carbonaceous coating; and is placed in a stream The nanocrystals exit the processing chamber and flow toward the substrate; a polymer conjugate is added to the stream to form a deposition mixture; and the deposition mixture is deposited on the substrate. Other embodiments provide an apparatus for forming an electrochemical film on a substrate, the apparatus having a processing chamber divider enclosing the substrate support and the dispenser having a drying chamber in fluid communication with the source of the precursor and the source of combustible mixture; an ignition source, Coupling to the drying chamber; and the splicing spray raft, disposed adjacent to the substrate support and spaced apart from the dispenser. Other embodiments provide a substrate transporter for forming an electrochemical film on a conductive surface of a substrate, and a substrate transporter having a continuous movement, and the substrate is configured to include a nanocrystal forming chamber having a plurality of nozzles.崦边知太# > μ The two nozzles extend toward the substrate conveyor and point toward the substrate conveyor, and the direction perpendicular to the nanocrystal forming chamber is in fluid communication with one or more of the lightning and a Drive source; combustible gas source, coupled to the nanocrystal to form a cavity. β to, and a plurality of heads, arranged on the substrate conveyor attached
近並與複數個嗔嘴古& „ A 嘴有所間隔，各個頭自管道延伸以分配 第二前驅物。 【實施方式】 201112466 本文所揭露之實施例大致提供在基板上形成薄膜的方 法與設備。一實施例中，薄膜可為薄膜電池（諸如，Li_ 離子電池或超級電容元件）之電化學薄膜。將包括電化學 活性材料微粒之前驅物或前驅物之混合物提供至處理腔 室’可將能量施加至處理腔室使得前驅物或前驅物混合 物處於高溫狀態。高溫可自微粒產生奈米晶體，奈米晶 體可在基板表面上形成層或薄膜。 第1圖係根據本文實施例電連接至負載1 0 i之Li_離子 電池1 00之示意圖。Li-離子電池！ 00之基本功能部件包 括陽極結構102、陰極結構103、分隔層1〇4及電解質（未 顯示）’配置於相對集電器i u與u 3間之區域中。可利 用多種材料作為電解質，例如有機溶劑或聚合基質（其亦 可由有機溶劑所浸透）中之鋰鹽。電解質係存在於陽極結 構102、陰極結構1〇3、與集電器ln與113間形成之區 域中的分隔層104中。 陽極結構102與陰極結構1〇3各自作為u離子電池 100之半電池（half-cell)，並一起形成u離子電池1〇〇 之完整工作電池（working ceU)。陽極結構1〇2包括集電 器111與帛含電解質材料11 G(例如，保留鐘離子之碳 系嵌合主體材料）。同樣地，陰極結構1〇3包括集電器ιΐ3 與保留經離子之第二含電解質材料ιι2(例如，金屬氧化 物）。集電益111與113係由導電材料（例如，金屬）所構 成。某些實例巾’分隔層i 〇4係介電、多孔、流體-可穿 透的層’其可用來避免陽極結構m與陰極結構ι〇3中Closely and spaced apart from a plurality of mouths, each of the heads is extended from the pipe to distribute the second precursor. [Embodiment] 201112466 The embodiments disclosed herein generally provide a method of forming a film on a substrate. In one embodiment, the film may be an electrochemical film of a thin film battery such as a Li-ion battery or a super-capacitor element. A mixture comprising precursors or precursors of electrochemically active material particles may be provided to the processing chamber. Applying energy to the processing chamber causes the precursor or precursor mixture to be at a high temperature. The high temperature can produce nanocrystals from the microparticles, and the nanocrystals can form a layer or film on the surface of the substrate. Figure 1 is an electrical connection according to embodiments herein. Schematic diagram of Li_ion battery 100 to load 1 0 i. Li-ion battery! The basic functional components of 00 include anode structure 102, cathode structure 103, separator layer 〇4, and electrolyte (not shown). In the region between the electrical appliances iu and u 3. A variety of materials can be used as electrolytes, such as organic solvents or polymeric matrices (which can also be used by organic solvents). The lithium salt in the impregnation. The electrolyte is present in the separator layer 104 in the region formed between the anode structure 102, the cathode structure 1〇3, and the current collectors ln and 113. The anode structure 102 and the cathode structure 1〇3 each serve as u The half-cell of the ion battery 100, and together form a complete working battery (working ceU) of the u-ion battery. The anode structure 1〇2 includes the current collector 111 and the electrolyte-containing material 11 G (for example, retained) The carbon of the bell ion is a chimeric host material. Similarly, the cathode structure 1〇3 includes a current collector ιΐ3 and a second electrolyte-containing material ιι2 (for example, a metal oxide) which retains ions. The collectors 111 and 113 are Conductive material (eg, metal). Some example towels 'separation layer i 〇 4 is a dielectric, porous, fluid-penetable layer' which can be used to avoid anode structure m and cathode structure ι〇3
S 201112466 之部件直接電接觸。The components of S 201112466 are in direct electrical contact.
Li-離子電池1 〇〇之陰極側或正電極上之電化學活性材 料可包括含鋰金屬氧化物’諸如鋰鈷二氧化物（LiC〇〇2) 或鐘猛二氧化物（LiMn〇2)。在正電極上形成一層之含電 解質材料可由氧化物類經姑氧化物、撖欖石類裡鐵填酸 鹽或尖晶石類鋰錳氧化物（LiMg204)所構成。非-鋰實施 例中’示範性陰極可由TiSz (二硫化鈦）所構成。示範性 含链氧化物可為一或多層的鋰鈷氧化物、或混合的金屬 氧化物，諸如LiNixC〇l-2xMn02、LiMn204。示範性磷酸 鹽可為鐵撖欖石（LiFeP〇4)與其變體（例如， [LlFei-x]yMgP〇4)、LiMoP04、LiCoP〇4、Li3V2(P〇4)3、 Ι^ν〇Ρ〇4、LiMP2〇7或LiFe15P2〇7。示範性氟磷酸鹽可 為 LiVP〇4F、LiA1P〇4F、Li5V(p〇4)2F2 、The electrochemically active material on the cathode side or the positive electrode of the Li-ion battery 1 may include a lithium-containing metal oxide such as lithium cobalt dioxide (LiC〇〇2) or bellocal dioxide (LiMn〇2). . The electrolyte-containing material forming a layer on the positive electrode may be composed of an oxide such as a sulphide oxide, a sulphate-based iron-salt or a spinel-based lithium manganese oxide (LiMg204). In the non-lithium embodiment, the exemplary cathode can be composed of TiSz (titanium disulfide). Exemplary chain oxides can be one or more layers of lithium cobalt oxide, or a mixed metal oxide such as LiNixC〇l-2xMnO 2, LiMn204. An exemplary phosphate may be ferrocene (LiFeP〇4) and its variants (eg, [LlFei-x]yMgP〇4), LiMoP04, LiCoP〇4, Li3V2(P〇4)3, Ι^ν〇Ρ 〇4, LiMP2〇7 or LiFe15P2〇7. Exemplary fluorophosphates can be LiVP〇4F, LiA1P〇4F, Li5V(p〇4)2F2,
Ll2CoP〇4F 或 Li2NiP〇4F。示範性矽酸鹽可為 Li2FeSi〇4、Ll2CoP〇4F or Li2NiP〇4F. An exemplary citrate can be Li2FeSi〇4,
Li2MnSi〇4或Li2VOSi04。示範性非-鋰化合物係Li2MnSi〇4 or Li2VOSi04. Exemplary non-lithium compound system
Na5V2(p〇4)2F3。Na5V2(p〇4)2F3.
Li離子電池i 〇〇之陽極側或負電極上之電化學活性材 料可由上述之材料（即，散佈於聚合物基f中之石墨微珠） 成此外可與石墨微珠共同使用或取代石墨微珠 來使用石夕、錫或鈦酸鐘（Li4Ti5〇|2)微珠來提供導電核心陽 極材料。 第^係總結根據—實施例之方法200的流程圖。方 係用來在基板上形成電化學劑（諸如，上述之電化 學活性材料、陰極與/或陽極材料)層。如上參照第1圖 201112466 所述’基板的表面包括電池結構之導電集 言，基板可具有鋼或鋁電極表面。步驟2〇 “列而 將第-前驅物提供至處理腔室(例如， 過管道 第3圖的加熱腔室则），腔室可為^^下^ 4圖與第5A圖分別之分配器-與5。4)之腔室。第= 驅物包括攜帶媒介中之電化學材料的散佈微粒（其= 直徑約Inm與約100nm間之奈米微粒)。微粒通常包括 用來形成上述電化學活性材料、陰極與/或陽㈣料的成 分。沉積於基板表面上且包含電化學材料之層於下文中 視為沉積層一實施射’攜帶媒介可為在進人處理腔 室之前與惰氣（諸如，氬、氦或氮）在高速下共同流過小 開口而霧化之液體。攜帶媒介亦可圍繞電化學奈米微粒 :集以降低附著至處理腔室壁。適當的液體攜帶媒介通 常包括氧’且包括水與有機液體（例如，醇）。液體攜帶 媒介通常在約2(TC與約50。(：間之溫度下具有低黏性（例 如，約1 0 cP或更低）以提供合理的霧化。 步驟204，將能量施加至第一前驅物以提高其之溫度 並活化結晶處理、自散佈於第一前驅物中之微粒形成奈 米Ba體。能望：激發散佈於第一前驅物中之微粒内的原子 熱移動’促使原子移動以優先發現較低能量的晶格位 置。一實施例中，能量為放熱反應產生之熱能。可添加 反應性混合物至第一前驅物以促進熱反應。舉例而言， 可添加氧至霧化氣體’並添加含碳流體至液體攜帶媒介。 某些實施例中’以電化學奈米晶體將碳沉積於基板上 10 201112466 係有利的。碳可作為沉積層之接合物，且碳之導電性可 改善薄膜性旎。透過攜帶媒介添加碳亦可避免處理過程 中電化學材料微粒的蒸發。可藉由利用含碳氣體（例如， 碳氫化合物，諸如甲烷（eh)或乙炔（(：汨2))而額外將碳添 加至〉儿積層。反應混合物中之過量碳將形成非晶碳微 粒，其將保留於沉積層中。過量碳亦可提供避免或妨礙 金屬氧化的還原環境。 微粒在反應區域中之停留時間與熱傳輸進入微粒之速 率係適以不需蒸發微粒而讓微粒結晶，且控制微粒尺寸 與微粒尺寸分佈。停留時間亦受到控制以在基板上提供 適當的沉積速率。熱傳輸進入微粒之速率亦由所應用之 特疋混合物及前驅物材料中成分的熱容所影響。舉例而 言’若需要的話’可應用較高級的碳氫化合物、共軛碳 氣化合物、或較冷的燃燒部分氧化燃料（例如，醇）以在 較緩慢的速率下提供熱輸入。此外，應用具有較高黏性 之攜帶媒介來形成微粒上的較厚覆蓋物、或應用具有較 低導熱性之攜帶媒介可降低熱輸入至微粒。具有高潛熱 之構帶媒介（例如’水）亦可控制熱輸入至微粒。 步驟206 ’將藉由施加能量至散佈於第一前驅物中之 微粒而形成之奈米晶體流（stream)引導離開處理腔室至 基板’以在基板上形成薄膜。藉由設計準確的流動圖案、 及處理腔至相對基板表面之移動、及經活化之前驅物離 開處理腔室或分配器之口的幾何形狀，以根據任何所欲 之圖案來散佈奈米晶體。 201112466 步驟208»當奈米晶體朝向基板移動時，第二前驅物 在處理腔至外與奈米晶體流混合。第二前驅物通常係提 供來促進將奈米晶體接合至基板。第二前驅物可包括接 合劑（例 聚合物）以固持奈米晶體於基板表面上。接 合劑-般而言具有少許導電性以避免減弱沉積層之性 忐。-實施例中’接合劑係以低於每個奈米晶體約⑽ 聚合物分子的比例來提供之低分子量含碳聚合物。低分 子量聚合物的數目平均分子量係低於約ι〇〇〇〇以促進夺 米微粒附著至基板。聚合物分子與奈米晶體之比例在晶 體間提供空間並促進附著而不妨礙電子與離子通過沉積 層之實質上自由路徑。 日步驟210，將奈米晶體與接合劑沉積於基板上。最小 1的接合劑佔用奈米晶體間之空隙以將奈米晶體附著至 薄臈’同時允許電子與離子自由流動通過沉積層。某些 =施例中’在薄膜形成過程中加熱基板以在接合劑及與 奈米晶體-同沉積之任何殘餘碳變硬之前促進奈米晶體 的緊达、配置。只要接合媒介未變成太抵抗移動的話，來 自處理腔室之奈米晶體的隨後碰撞可促進奈米晶體的緊 密配置。 ' 第3圖係根據一實施例之處王里腔g 3〇〇的#意橫剖面 圖。處理腔室300包括封圍件3〇2、基板支撐件3〇4、及 分配器306,分配器306用以朝向配置於基板支撐件3〇4 上之基板提供經活化之材料328。若想要的話，分配器 6(其可為依照所欲圖案分配奈米晶體之分散器）包括 J2 201112466 第一腔室308、第二腔室312、及提供接合物之管道32〇。 第一腔室308的内部310係流體連通於第一進入口；π 6, 而第一前驅物.混合物流過第一進入口 316。第一進入口 316係藉由第一源管道338通過流動控制器336而流體 連通於第一前驅物源（未顯示）《第一進入口 316的尺寸 係經設計’以在若第一前驅物混合物與霧化氣體在高速 下流過第一進入口 3丨6時霧化第一前驅物混合物。 第一開口 324可讓前驅物自第一腔室3〇8流至第二腔 室312。第二腔室312的内部314係流體連通於第一腔 室308與第二進入口 318，第二進入口 318用以提供可 燃混合物至第二腔室3丨2。藉由點火源3 3 4點燃可燃混 合物’點火源可為配置在第二腔室312之出口 326附近 的火化產生器。燃燒反應產生之熱能可乾燥電化學材料 之散佈微粒並將其結晶化成奈米晶體。分配器3〇6可經 運作以致在前驅物微粒沉積於基板表面上之前、或者部 分地在沉積之前且部分地在沉積之後，前驅物微粒在第 一腔室312中、第二腔室312外（移動至基板時）結晶。 某些實施例中，亦可將電能耦接至第一腔室與/或第二腔 室之壁以促進熱再結晶處理。 通過第二開口 326離開分配器3〇6之混合物包括即將 積於基板上之奈米晶體流3 2 8，且係由通常包括燃燒 產物之氣體混合物所攜帶。氣體混合物通常包含水蒸 汽、一氧化碳與二氧化碳、及微量的蒸發電化學材料（例 如，金屬）。至少某些奈米晶體亦可部分地或完全地由含 13 201112466 碳材料所含碳材料可衍生自與奈米微粒前驅物共 同提供之攜帶媒介的燃燒。一實施例中，氣體混合物包 括非反應性載氣成分（諸如，氩（Ar)或氮，其係用來 助於輸送經活化之材料至基板表面。 管道320係設以提供第三前驅物以與撞擊基板表面之 奈米晶體流328混合。第三前驅物可為接合劑、填充劑、 導電度促進劑、或其之任何一者或全部。某些實施例中， 第三前驅物係提供至經活化之材料與基板表面間之接觸 位置附近的可喷塗聚合物（其可為聚合物溶液或漿狀 物）。 第二與第二前驅物之流動亦由控制器3 3 6所控制，控 制器336亦可設以藉由調整含碳氣體之流率來管理反應 混合物中之碳總量與/或反應溫度。 另一實施例中’可與第一前驅物一起來提供接合物。 舉例而言’第一前驅物可包括水中金屬氧化物微粒的漿 狀物其具有醣類與醇類以提供碳。接合物（例如，聚丙 烯酸）可與水性第一前驅物混合，其接著提供至分配器之 燃燒區。將微粒乾燥與再結晶化，而聚丙烯酸與非晶碳 微粒在奈米晶體周圍聯合以形成沉積喷塗物。沉積喷塗 物保持熱到足以維持聚合物接合物在彈性狀態，直到奈 米晶體沉積於基板上為止，之後聚合物接合物隨著薄膜 冷卻而凝固。 一實施例中，活化腔室包括噴嘴，前驅物混合物可經 由噴嘴離開而進入混合區。第4圖係根據另一實施例之 201112466 設備4 0Ό之示意橫為丨；的 、。面圖。設備4〇〇包括處理腔室402、 基板支撐件404及分Β 刀配4〇6(某些實施例中，其可為根 據某些所欲圖案分配材料之分散器）。 分配器406包括笛Λ 第一腔至408及喷嘴42〇，前驅物混 合物經由喷嘴離開分配哭 刀配器406。通過第一口 412將前驅 物混合物提供至第—將宝4Λβ 咏 ^ 卜 腔至408 ,第一口 412係透過第一 管道436流體連通於俞艇μ ^ ^ 於則驅物源（未顯示），且流率係由流 動控制器434所控制。筮 „ , , 制第一口 412可包括液體、漿狀物 或懸浮前驅物之霧化II。戒# d。 務化器噴嘴42 0自第一腔室408通過 開口 4 1 8攜帶前驅物混人物$疮 此0物至噴嘴420末端附近的混合 區域4 2 2。 展口區域422可為活化腔室彻附近之封圍件或邊緣 空間，設以用所欲圖案引導氣體混合物朝向基板。一實 例中透過圍繞喷嘴420之環狀路徑428提供可燃混合 物環狀路& 428係设以在經活化之前驅物離開喷嘴㈣ 時將可燃混合物以均勻方式流入經活化之前驅物。當可 燃混合物與經活化之前驅物混合時，混合區域—中發 生之燃垸反應產生熱與壓力以將前驅物材料結晶成奈米 晶體’蒸發液體攜帶媒介、並推動奈米晶體流向外成散 佈圖案而至基板支撐件404。喷嘴42〇與混合區域422 之準確幾何形狀可經調整以達成任何所欲之流動圖案或 混合方法。言史言十準確《混合方法有助於控熱輸送進入 奈米晶體。舉例而言，包含可燃氣體與經活化之前驅物 之渦流的混合方法有助於控制來自燃燒反應之熱量應用 15 201112466 至奈米晶體。 分配器406更包括第二管道414,可經由第二管道414 提供可燃氣體混合物至混合區域422 ;及第三管道424， 可經由第三管道424提供第三前驅物。第三前驅物係提 供用來在奈米晶體撞擊配置於基板支撐件上之基板時與 奈米晶體在分配器406外混合，基板支撐件係配置於腔 室402之處理區432中。第三管道424可具有分配頭， 其設以分配第二前驅物成與基板上經活化之材料撞擊之 圖案實質重疊的圖案，以致奈米晶體由第二前驅物固持 於基板上。 第4圖之設備中，分配器406相對於基板支撐件404 移動以在配置於基板支撐件4〇4上之基板的所有或一 實質邛/7上形成薄膜。這可藉由移動分配器、基板 支撐件404或兩者而加以達成。第4圖[分配器係設 以利用致動器444而橫跨腔室4〇2延伸與縮回，致動器 444可為準確x、y平台。 排出氣體通過排 430(其可具有任何習知結構）離 開腔室402。如第4圔祕_ Α 之 〇α第4圖所不般，排出口 430可為腔室402 圍繞腔=二:配Ϊ者可為多個上述開° ’或者可為 括微粒捕捉器428，二之'邊排。出通道。排出口 430包 達真办 1避免分配器406所產生之微粒到 似可：及腔室.4〇2下游的其他處理裝置。微粒捕捉器 運作中壬：適當的裝置，例如過濾器或渦流分離器。 可將電池之電化學層沉積於基板上但將基板 16 201112466 配置於基板支料4G4且建立可燃氣體混合物至^區 422之流動。•點火源426可用來點燃可燃混合物 整可燃混合物之流率以維持燃燒反應。接著透過第 室傷建立前驅物混合物至混合區之流動，第一腔室_ 可允許第一前驅物之霧化。流動控制器調整可燃氣體 合物之流動與組成以維持混合區中之溫度，可利用样： 溫度感應器(未顯示則測溫度。若利用分隔的接：物 材料流的is ’那麼透過口 424建立接合物材料流以 電化學層。 第5A圖係根據另一實施例之設備的示意橫剖面 圖。如同第3圖與第4圖之設備，設備5〇〇包括分配器 5〇4及基板支撐件502 (第5A圖未顯示腔室封圍件）。第 5A圖之設備中，分配器5〇4包括複數個流體連通於活化 腔至506之内冑508的喷嘴524。透過管道532提供包 含即將沉積於基板上之經活化材料的沉積前驅物⑷ 如上述之那些前驅物），管道532係流體連通於一或多 個/儿積刖驅物源’且其特徵為液體前驅物之霧化器。可 如同第3圖與第4圖所示般利用耦接至活化腔室506之 壁的電％產生器（未顯示）來執行活化。若有需要的話， 可如同本文所述之其他實施例般應用絕緣體來控制並隔 離應用至活化腔室506之電場。 、’i /舌化之材料通過第一開口 522離開活化腔室5〇6進 嘴f 524並接著通過第二開口 526進入各個喷嘴524 外形成之展合區528。可利用管冑534通過喷嘴524提 17 201112466 供可燃混合物至混合區528，管道534係流體連通於氣 體腔至5 12及可燃氣體源（未顯示）^如參照本文所述其 他實施例所述，經活化之材料與可燃混合物之混合觸發 釋放熱此之燃燒反應，其造成經活化之材料以喷塗圖案 53〇朝向基板502傳遞。一形態中’經活化之材料中之 月J驅物微粒在沉積於基板表面上之前結晶化形成奈米晶 體。藉由噴嘴幾何形狀與氣流速度與燃燒反應速度來構 形嘴塗圖案530，以覆蓋配置於基板支撐件5〇2上之基 板的實質部分。類似於上述’透過管道536提供第二前 驅物，管道536係流體連通於口 518與一或多個第二前 驅物源。在經活化之材料流以喷塗圖案53〇朝向基板5〇2 傳遞時口 5 1 8之結構係經設計以混合第二前驅物與經 活化之材料流，導致成分（例如，奈米晶體）撞擊於基板 502上時形成於與/或結合至基板5〇2上。 或者，具有多個喷嘴之分配器（例如，分配器5〇4)可將 所有喷嘴設置成線性結構、或任何其他習知結構。爲了 達到平面基板的完全覆蓋’可根據與上述相似之方法在 喷塗經活化之材料時移動分配器橫跨基板、或者可在分 配器下移動基板、或者上述兩者方式均有。第5B圖係設 備540之示意側視圖，其設以沿著輸送器550移動基板 通過處理腔室’處理腔室具有橫跨輸送器550之輸送路 徑而配置之分配器504。基板通過第一開〇如進入腔 室並移動至預熱器別下方，預熱器別加熱基板至選 擇之目標溫度以藉由增進沉積層附著至基板來提高電化 18 201112466 學薄膜_ # 之，_、、》成。分配器504之多個喷嘴定向成橫跨基板 之=徑μ在基板移動到分配器下方時均勻地覆蓋基板。 、节藉由水平致動器（例如，第5Β圖示意呈現之滾輪⑽) 來移動輸送器。已經以電化學薄膜覆蓋之基板通過第二 開口 564離開腔室以進行進一步處理。 •,。圖係第5Α圖之設備的放大圖，基板575係配置 ;輸史器550上以進行處理。當基板575被攜帶朝向第 開564時，分配器5〇4分配材料以在基板575上形 成沉積層580。當基板575移動至分配器5()4下方時， /儿積層58G自基板575之—邊緣朝向另—邊緣生成。 第5D圖係根據另一實施例之設備595的示意平面圖。 設備595特徵為輸送器584在面對兩個相對分配器577a 與577B之方向中輸送基板575。分配器577A與5 77B 各自大致符合第4圖之分配器4〇6的描述。分配器577A 與577B。各自架设於各個定位器585a與如b，其可為線 性定位器或x-y定位器。控制器59〇控制定位器5“與 分配器577之運作以同時或同步地以接合物t之電化學 材料塗覆基板575之兩個主要表面。 -貫施例中，在熱喷塗運作中將電化學活性材料層沉 積於基板上。將包括水漿狀物巾電化學活㈣料（例^， 經金屬氧化物’其可為本文所述之任何電化學活性化合 物或其之混合物)之微粒的電化學沉積前驅物材料暴： 於熱能’以形成沉積於基板上之電化學活性奈米晶體 流。漿狀物可與含碳流體（例如，包括氧與氫之有機化合 201112466 物’例如異丙醇）混合以形成前驅物混合物。可如上述般 將糖類溶解於水攜帶媒介以添加碳至混合物。 衆狀物實施例中’在約5 mL/min與約1 〇〇 mL/min間 (例如，約50 mL/min)之流率下將前驅物混合物流入處理 腔至（可為乾燥腔室），並利用來自燃燒反應之熱能乾 燥。通常在約10 psi與約30 psi間之壓力下，以載氣霧 化前驅物混合物，載氣諸如氮氣（A)、氫氣（H2)、氦（He)、 氬（Ar)、或其之混合物。若有需要的話，亦可用氧或空 氣作為霧化氣體以促進燃燒。應用氧或空氣作為霧化氣 體可讓燃料氣體個別地供應至分配器，燃料與氧僅在分 配器之反應區域中混合。 將可燃氣體混合物提供至分此甘跑埤干斗” 而言，可將氧與一或多個碳氫化合物（諸如，曱烷、乙烷' 乙炔、丙烷或另-燃料)之混合物添加至前驅物混合物或 分離地提供至處理腔室。或者，可添加氧或空氣至前驅 物混合物並透過分隔的管道提供碳氫化合物。可_氣體 混合物係經反應以提供形成奈米晶體之熱能。熱能蒸發 反應混合物中任何殘餘液體並再結晶化電化學前驅物以 形成離開處理腔室且移向基板之奈米晶體流。 可添加過量碳至反應現合物以促進在奈米晶體上形成 含碳塗層。過量碳在奈米晶體 〜战時凝聚於奈米晶體周 圍’並提供熱絕緣給形成之夺平曰触 不…卡日曰體以避免形成之奈米 曰曰體上任何不欲之熱影響。可益 精由調整反應混合物中過 量碳的數量來控制能量輸入電化風& 予則驅物與/或腔室溫 20 201112466 度。過量碳的比熱自燃燒混合物吸收一部分的熱能，而 奈米HB體上較厚的碳塗層可降低熱輸入至奈米晶體。此 外，最終薄膜中之碳沉積可改善薄膜之電特性並促進奈 米晶體附著至基板。由於氫與反應混合物中之氧反應之 故’含氫載氣亦可用來控制腔室中之溫度。處理腔室中 之溫度通常維持在約6〇〇〇c與約15〇(rc之間例如約 8〇〇°C與約i，20(rc之間，例如約1〇〇〇ec。 前驅物混合物包括通式為LiNiwMgxC〇y〇z之電化學活 性材料，其中w、X與Υ各自在約0.3與1 ·5之間而z係 在約1.5與2.5之間。奈米晶體由一熱氣體流帶出處理腔 至 貫施例中，奈米晶體在約100 mm/sec與約600 mm/sec間（例如，约3〇〇 mm/sec)之速率下離開處理腔 室。流形成長度在約〇.丨與i 5 m間（例如，約i⑺）之喷 射物。通常將基板配置於離開處理腔室約〇丨與丨5爪間。 將接合物注入離開處理腔室之流中。接合物通常為促 進奈米晶體附著至基板之聚合物，且接合物在某些實施 例中亦可提供某些所欲之電特性。通常以液體（諸如，溶 液、懸浮液或乳狀液）來提供接合物。一實施例中，接合 物為水乳狀液中之變性苯乙烯_丁二烯橡膠材料。接合物 前驅物之流率通常為至處王里⑮室之電化學前驅物流率的 約1 0%與㉝75%之間’例如約3()%。在針對其之能量含 量選擇之位置混合接合物與奈米晶體流。奈米晶體流中 之殘餘熱量可蒸發溶劑或液體的連續相，可讓接合物自 由地接觸奈米晶體。處理腔室出口與基板共同界定奈米 21 201112466 晶體噴塗距離， 定接合物 處腔室出σ與接合m點共同界 在奈米晶體：距離。大多數實例中，接合物注入距離係 與約8〇%之間塗距離的約6〇%與約9〇%之間，例如約7〇% 其之组^驅物可為任何本文所述之電化學活性物種或 a . __ 大多數實例中，電化學活性前驅物包括鋰， I :匕括鎳、鎂、鈷或其之混合物。不同的電化學前 之鋰二二來Z儿積具有不同特徵之層。可藉由沉積富含鎳 么土料來形成高容量層。利用上述通式，若W係大 ;、〇則儿積層將為高容量層。若χ與y各自高於約 則'儿積層將為高穩定性層。某些實施例中可藉由 在沉積過程中改變電化學前驅物之成分來沉積複合層。 藉由在^積過程不同時間點上提供不同的前驅物，可形 成具有高容量核心與高穩定性外層之複合層。 雖然上述係針對本發明之實施例，但可在不障離本發 明之基本|&圍下設計出本發明之其他與更多實施例。 【圖式簡單說明】 為了更詳細地了解本發明之上述特徵，可參照實施例 (某些描繪於附圖中）來理解本發明簡短概述於上之特定 描述。然而，需注意附圖僅描繪本發明之典型實施例而 因此不被視為其之範圍的限制因素，因為本發明可允許 其他等效實施例。 22 201112466 第1圖係根據一實施例之Li-離子電池的示意圖。 第2圖係總結根據一實施例之方法的流程圖。 第3圖係根據一實施例之薄膜形成設備的示意橫剖面 圖。 第4圖係根據另一實施例之薄膜形成設備的示意橫剖 面圖。 第5Α圖係根據另一實施例之薄膜形成設備的示意橫 剖面圖。 第5Β圖係根據另一實施例之薄膜形成設備的示意側 視圖。 第5C圖係第5Α圖之設備的放大圖。 第5D圖係根據另一實施例之設備的示意平面圖。 爲了促進理解，盡可能應用相同的元件符號來標示圖 示中相同的元件。預期一實施例揭露之元件與特徵可有 利地用於其他實施例而不需特別詳述。 【主要元件符號說明】 100 L i -離子電池 101 負載 102 陽極結構 103 陰極結構 104 分隔層 110 第一含電解質材料 111 ' 113 集電器 112 第二含電解質材料 200 方法 202 ' 204 ' 206 ' 208 、 210 步驟 23 201112466 300 ' 402 處理腔室 302 封圍件 304 ' 404、502 基板支撐件 306、 406 、 504 、 577A 、577B 分配器 308 ' 408 第一腔室 310、 314 ' 508 内部 3 12 第二腔室 3 16 第一進入口 318 第二進入口 320 ' 532 ' 534 > 536 324 ' 522 、 562 第一 開口 326 ' 526 、 564 第二 開口 328 奈米晶體流 334、 426 點火源 336、 434 流動控制器 338 第一源管道 400 ' 500 ' 540 ' 595 設備 412 第一口 414 第二管道 418 開口 420 ' 524 喷嘴 422 混合區域 424 第三管道 428 微粒捕捉器 430 排出口 432 處理區 436 第一管道 444 致動器 506 活化腔室 512 氣體腔室 518 口 528 混合區 530 喷塗圖案 550、 584 輸送器 560 滚輪 570 預熱器 575 基板 580 沉積層 585A ' 5 85B 定位器 590 控制器 管道 24The electrochemically active material on the anode side or the negative electrode of the Li ion battery i may be formed from the above materials (ie, graphite beads dispersed in the polymer group f) or may be used together with or substituted for the graphite beads. The use of Shixi, tin or titanic acid clock (Li4Ti5〇|2) beads to provide a conductive core anode material. The summary of the method 200 according to the embodiment is summarized. The layer is used to form a layer of an electrochemical agent (such as the electrochemically active material, cathode and/or anode material described above) on the substrate. As described above with reference to Fig. 1 201112466, the surface of the substrate includes a conductive layer of a battery structure, and the substrate may have a steel or aluminum electrode surface. Step 2: "List the first precursor to the processing chamber (for example, through the heating chamber of Figure 3 of the pipeline), the chamber may be a separate distributor of the ^^^4 and 5A respectively - And the chamber of 5.4). The precursor comprises a dispersed particle carrying an electrochemical material in the medium (which = nanometer particles having a diameter of about Inm and about 100 nm). The microparticles generally include the electrochemical activity described above. The composition of the material, the cathode and/or the cation (four) material. The layer deposited on the surface of the substrate and comprising the electrochemical material is hereinafter referred to as the deposition layer. The carrier medium can be inert to the chamber before entering the processing chamber ( Liquids such as argon, helium or nitrogen that flow together through small openings at high speeds. The carrier medium can also surround the electrochemical nanoparticles: to reduce adhesion to the walls of the processing chamber. Suitable liquid carriers typically include oxygen. 'And includes water and organic liquids (eg, alcohols). Liquid carrier media typically provide a low viscosity (eg, about 10 cP or less) at about 2 (TC) and about 50. Atomization. Step 204, applying energy to the first precursor In order to increase the temperature and activate the crystallization treatment, the particles dispersed in the first precursor form a nano Ba body. It is expected that the atomic heat movement in the particles dispersed in the first precursor is excited to promote atomic movement to give priority. A lower energy lattice position is found. In one embodiment, the energy is thermal energy generated by an exothermic reaction. A reactive mixture can be added to the first precursor to promote thermal reaction. For example, oxygen can be added to the atomizing gas' Adding a carbonaceous fluid to the liquid carrier. In some embodiments, 'carbon is deposited on the substrate as an electrochemical nanocrystal. 10 201112466 is advantageous. Carbon can act as a bond to the deposited layer, and carbon conductivity improves the film. The addition of carbon through the carrier medium also avoids evaporation of electrochemical material particles during processing by utilizing carbon-containing gases (eg, hydrocarbons such as methane (eh) or acetylene ((: 汨 2)). Additional carbon is added to the layer. The excess carbon in the reaction mixture will form amorphous carbon particles, which will remain in the deposited layer. Excess carbon can also provide or avoid metal The reduction environment of the particles in the reaction zone and the rate of heat transfer into the particles are suitable for crystallizing the particles without evaporating the particles, and controlling the particle size and particle size distribution. The residence time is also controlled on the substrate. Providing an appropriate deposition rate. The rate at which heat is transported into the particles is also affected by the heat capacity of the constituents of the particular mixture and precursor materials used. For example, 'if needed' can apply higher hydrocarbons, a conjugated carbon gas compound, or a relatively cold burning partially oxidized fuel (eg, an alcohol) to provide heat input at a slower rate. Further, a carrier having a higher viscosity is used to form a thicker covering on the particles, Or use a carrier medium with lower thermal conductivity to reduce heat input to the particles. A belt medium with high latent heat (such as 'water) can also control heat input to the particles. Step 206' directs a stream of nanocrystals formed by applying energy to the particles dispersed in the first precursor away from the processing chamber to the substrate ' to form a thin film on the substrate. The nanocrystals are dispersed according to any desired pattern by designing an accurate flow pattern, and movement of the processing chamber to the opposite substrate surface, and the geometry of the opening of the processing chamber or dispenser prior to activation of the precursor. 201112466 Step 208»When the nanocrystal moves toward the substrate, the second precursor mixes with the nanocrystal stream outside the processing chamber. A second precursor is typically provided to facilitate bonding of the nanocrystals to the substrate. The second precursor may include a binder (e.g., a polymer) to hold the nanocrystals on the surface of the substrate. The bonding agent - in general, has little conductivity to avoid weakening the properties of the deposited layer. - In the examples, the binder is a low molecular weight carbon-containing polymer provided at a ratio of about (10) polymer molecules per nanocrystal. The low molecular weight polymer has a number average molecular weight of less than about 1 Å to promote adhesion of the smear particles to the substrate. The ratio of polymer molecules to nanocrystals provides space between the crystals and promotes adhesion without hindering the substantial free path of electrons and ions through the deposited layer. In step 210, a nanocrystal and a bonding agent are deposited on the substrate. A minimum of 1 binder occupies the interstices between the nanocrystals to attach the nanocrystals to the thin 臈' while allowing electrons and ions to flow freely through the deposited layer. Some = in the example 'heats the substrate during film formation to promote the tightness and configuration of the nanocrystals before the bonding agent and any residual carbon deposited with the nanocrystals become hard. The subsequent collision of the nanocrystals from the processing chamber promotes the tight configuration of the nanocrystals as long as the bonding medium does not become too resistant to movement. 'Fig. 3 is a cross-sectional view of the cross section of the Wangli cavity g 3〇〇 according to an embodiment. The processing chamber 300 includes a sealing member 3, a substrate support member 3, 4, and a dispenser 306 for providing an activated material 328 toward a substrate disposed on the substrate support member 3''. If desired, the dispenser 6 (which may be a disperser that dispenses nanocrystals in accordance with the desired pattern) includes J2 201112466 first chamber 308, second chamber 312, and conduit 32 that provides the splicing. The interior 310 of the first chamber 308 is in fluid communication with the first inlet port; π 6, and the first precursor. mixture flows through the first inlet port 316. The first inlet port 316 is in fluid communication with the first precursor source (not shown) by the first source conduit 338 through the flow controller 336. "The size of the first inlet port 316 is designed to be in the first precursor. The mixture and the atomizing gas atomize the first precursor mixture as it flows through the first inlet port 3丨6 at a high speed. The first opening 324 allows the precursor to flow from the first chamber 3〇8 to the second chamber 312. The interior 314 of the second chamber 312 is in fluid communication with the first chamber 308 and the second inlet port 318 for providing a combustible mixture to the second chamber 3丨2. Ignition of the combustible mixture by the ignition source 336's ignition source may be a cremation generator disposed adjacent the outlet 326 of the second chamber 312. The thermal energy generated by the combustion reaction dries the dispersed particles of the electrochemical material and crystallizes them into nanocrystals. The distributor 3〇6 can be operated such that the precursor particles are in the first chamber 312 and outside the second chamber 312 before the precursor particles are deposited on the substrate surface, or partially before deposition and partially after deposition. Crystallization (when moving to the substrate). In some embodiments, electrical energy can also be coupled to the walls of the first chamber and/or the second chamber to facilitate thermal recrystallization. The mixture exiting the distributor 3〇6 through the second opening 326 includes a stream of nanocrystals 3 2 8 to be deposited on the substrate and carried by a gas mixture which typically includes combustion products. The gas mixture typically contains water vapor, carbon monoxide and carbon dioxide, and traces of evaporating electrochemical materials (e.g., metals). At least some of the nanocrystals may also be derived, in part or in whole, from the carrier medium provided by the carbon material comprising 13 201112466 carbon material, which may be derived from the carrier medium provided with the nanoparticle precursor. In one embodiment, the gas mixture includes a non-reactive carrier gas component, such as argon (Ar) or nitrogen, which is used to assist in transporting the activated material to the surface of the substrate. The conduit 320 is configured to provide a third precursor to Mixing with a nanocrystal stream 328 striking the surface of the substrate. The third precursor can be a bonding agent, a filler, a conductivity promoter, or any or all of them. In some embodiments, the third precursor is provided a sprayable polymer (which may be a polymer solution or slurry) near the contact position between the activated material and the surface of the substrate. The flow of the second and second precursors is also controlled by the controller 336 The controller 336 can also be configured to manage the total amount of carbon and/or reaction temperature in the reaction mixture by adjusting the flow rate of the carbonaceous gas. In another embodiment, the conjugate can be provided with the first precursor. For example, 'the first precursor may include a slurry of metal oxide particles in water that has sugars and alcohols to provide carbon. The conjugate (eg, polyacrylic acid) may be mixed with the aqueous first precursor, which is then provided To distributor Burning zone. Drying and recrystallizing the particles, and polyacrylic acid and amorphous carbon particles are combined around the nanocrystals to form a deposited spray. The deposited spray remains hot enough to maintain the polymer bond in an elastic state until The nanocrystals are deposited on the substrate, after which the polymer conjugate solidifies as the film cools. In one embodiment, the activation chamber includes a nozzle through which the precursor mixture exits into the mixing zone. Figure 4 is based on another An embodiment of the 201112466 device has a schematic cross-section of the device. The device 4 includes a processing chamber 402, a substrate support 404, and a bifurcation knife 4 (in some embodiments, The dispenser may be a dispenser that dispenses material according to certain desired patterns. The dispenser 406 includes a first chamber to 408 and a nozzle 42A, and the precursor mixture exits the dispensing chopper adapter 406 via the nozzle. The precursor is passed through the first port 412. The mixture is supplied to the first chamber 412 to the 408, and the first port 412 is in fluid communication with the Yu Chuan μ ^ ^ through the first conduit 436 to the source (not shown), and the flow rate is Controlled by the flow controller 434. The first port 412 can include a liquid, slurry or suspension precursor atomization II. ## d. The chemist nozzle 42 0 passes through the opening from the first chamber 408 4 1 8 carrying the precursor mixed character $ sore to the mixing area 4 2 2 near the end of the nozzle 420. The opening area 422 can be the enclosure or edge space near the activation chamber, set with the desired pattern The gas mixture is directed toward the substrate. In one example, the flammable mixture annulus & 428 is provided through an annular path 428 surrounding the nozzle 420 to allow the combustible mixture to flow in a uniform manner prior to activation prior to activation of the exiting nozzle (4). When the combustible mixture is mixed with the activated precursor, the combustion reaction occurring in the mixing zone generates heat and pressure to crystallize the precursor material into nanocrystals 'evaporating liquid carrier medium and propelling the flow of nanocrystals. The outer pattern is spread to the substrate support 404. The exact geometry of the nozzle 42A and the mixing zone 422 can be adjusted to achieve any desired flow pattern or mixing method. The history of the words is accurate. The hybrid method helps to control the heat transfer into the nanocrystals. For example, a mixing method comprising vortex of combustible gas and activated precursors helps control the heat application from the combustion reaction 15 201112466 to nanocrystals. The distributor 406 further includes a second conduit 414 that provides a combustible gas mixture to the mixing region 422 via a second conduit 414; and a third conduit 424 that provides a third precursor via the third conduit 424. The third precursor is provided for mixing the nanocrystals outside the dispenser 406 when the nanocrystals strike the substrate disposed on the substrate support, the substrate support being disposed in the processing region 432 of the chamber 402. The third conduit 424 can have a dispensing head that is configured to dispense a pattern in which the second precursor substantially overlaps the pattern of impact with the activated material on the substrate such that the nanocrystals are retained by the second precursor on the substrate. In the apparatus of Fig. 4, the dispenser 406 is moved relative to the substrate support 404 to form a film on all or a substantial 邛/7 of the substrate disposed on the substrate support 4〇4. This can be achieved by moving the dispenser, substrate support 404, or both. Figure 4 [Distributor is configured to extend and retract across chamber 4〇2 using actuator 444, which may be an accurate x, y platform. Exhaust gas exits chamber 402 through row 430 (which may have any conventional configuration). As shown in Fig. 4, the discharge port 430 may be a chamber 402 surrounding the cavity = two: the arranging device may be a plurality of the above-mentioned openings or may include a particle trap 428, Second's side row. Out channel. Discharge 430 bags to achieve the real thing 1 to avoid the particles generated by the distributor 406 to: and other processing devices downstream of the chamber.4〇2. Particle trapper In operation: Suitable devices, such as filters or eddy current separators. The electrochemical layer of the cell can be deposited on the substrate but the substrate 16 201112466 is disposed on the substrate support 4G4 and the flow of the combustible gas mixture to the region 422 is established. • Ignition source 426 can be used to ignite the flow rate of the combustible mixture to the combustible mixture to maintain the combustion reaction. The flow of the precursor mixture to the mixing zone is then established through the first chamber injury, and the first chamber _ can allow atomization of the first precursor. The flow controller adjusts the flow and composition of the combustible gas composition to maintain the temperature in the mixing zone. A sample is available: a temperature sensor (not shown, the temperature is measured. If the separation is used, the flow through the port 424) A flow of the conjugate material is established as an electrochemical layer. Figure 5A is a schematic cross-sectional view of the apparatus according to another embodiment. Like the apparatus of Figures 3 and 4, the apparatus 5 includes a dispenser 5〇4 and a substrate Support 502 (Fig. 5A does not show the chamber enclosure). In the apparatus of Fig. 5A, the distributor 5〇4 includes a plurality of nozzles 524 that are in fluid communication with the inner chamber 508 of the activation chamber 506. a deposition precursor (4) comprising an activated material to be deposited on a substrate, such as those described above, the conduit 532 being in fluid communication with one or more sources and characterized by a mist of liquid precursor Chemist. Activation can be performed using an electricity generator (not shown) coupled to the wall of the activation chamber 506 as shown in Figures 3 and 4. If desired, an insulator can be applied to control and isolate the electric field applied to the activation chamber 506 as in the other embodiments described herein. The 'i/tongue material exits the activation chamber 5〇6 through the first opening 522 into the nozzle f 524 and then through the second opening 526 into the flared region 528 formed outside each nozzle 524. Tube 534 may be utilized to provide a combustible mixture to mixing zone 528 through nozzle 524, conduit 534 being in fluid communication with gas chamber to 5 12 and a combustible gas source (not shown) as described with respect to other embodiments described herein, The mixing of the activated material with the combustible mixture triggers the release of heat from the combustion reaction which causes the activated material to be transferred toward the substrate 502 in a spray pattern 53. In one form, the J-dried particles in the activated material are crystallized to form nanocrystals before being deposited on the surface of the substrate. The mouth coating pattern 530 is configured by the nozzle geometry and the air flow velocity and the combustion reaction speed to cover a substantial portion of the substrate disposed on the substrate support 5〇2. Similar to the above ' providing a second precursor through conduit 536, conduit 536 is in fluid communication with port 518 and one or more second precursor sources. The structure of the port 518 is designed to mix the second precursor with the activated material stream as the flow of activated material is transferred toward the substrate 5〇2 by the spray pattern 53〇, resulting in a composition (eg, nanocrystals). When impinging on the substrate 502, it is formed on and/or bonded to the substrate 5〇2. Alternatively, a dispenser having multiple nozzles (e.g., dispenser 5〇4) can set all of the nozzles into a linear configuration, or any other conventional configuration. In order to achieve complete coverage of the planar substrate, the dispenser can be moved across the substrate when spraying the activated material, or the substrate can be moved under the dispenser, or both, in a manner similar to that described above. Figure 5B is a schematic side view of apparatus 540 that is configured to move the substrate along conveyor 550 through a processing chamber. The processing chamber has a distributor 504 disposed across the transport path of conveyor 550. The substrate passes through the first opening, such as entering the chamber and moving to the lower side of the preheater, and the preheater does not heat the substrate to the selected target temperature to improve the electrification by increasing the adhesion of the deposited layer to the substrate. _,,"to make. The plurality of nozzles of the distributor 504 are oriented across the substrate = diameter μ uniformly covering the substrate as the substrate moves below the dispenser. The section moves the conveyor by a horizontal actuator (for example, the roller (10) schematically illustrated in Figure 5). The substrate that has been covered with the electrochemical film exits the chamber through the second opening 564 for further processing. •,. The figure is a magnified view of the apparatus of Figure 5, with the substrate 575 being configured; the history 550 is used for processing. When the substrate 575 is carried toward the first opening 564, the dispenser 5〇4 dispenses material to form a deposited layer 580 on the substrate 575. When the substrate 575 is moved under the dispenser 5 () 4, the /-layer 58G is generated from the edge of the substrate 575 toward the other edge. Figure 5D is a schematic plan view of a device 595 in accordance with another embodiment. Device 595 is characterized by conveyor 584 conveying substrate 575 in a direction facing the two opposing dispensers 577a and 577B. The dispensers 577A and 5 77B each substantially conform to the description of the dispenser 4〇6 of Fig. 4. Distributors 577A and 577B. They are each mounted on respective locators 585a and b, which may be linear or x-y locators. The controller 59 controls the positioner 5 to "operate with the dispenser 577 to simultaneously or simultaneously coat the two major surfaces of the substrate 575 with the electrochemical material of the bond t. - In the embodiment, in the thermal spraying operation Depositing a layer of electrochemically active material onto the substrate. The slurry comprising the aqueous slurry will be electrochemically active (eg, via a metal oxide 'which can be any of the electrochemically active compounds described herein or mixtures thereof) Electrochemical deposition of particulate precursor material material: in thermal energy to form an electrochemically active nanocrystal stream deposited on a substrate. The slurry may be associated with a carbonaceous fluid (eg, including an organic combination of oxygen and hydrogen 201112466) Isopropanol) is mixed to form a precursor mixture. The sugar can be dissolved in a water carrying vehicle to add carbon to the mixture as described above. In the embodiment, between about 5 mL/min and about 1 〇〇mL/min The precursor mixture is flowed into the processing chamber (for example, a drying chamber) at a flow rate (e.g., about 50 mL/min) and dried using thermal energy from the combustion reaction. Typically between about 10 psi and about 30 psi Under the carrier The precursor mixture, a carrier gas such as nitrogen (A), hydrogen (H2), helium (He), argon (Ar), or a mixture thereof, may also be used as an atomizing gas to promote combustion if necessary. The use of oxygen or air as the atomizing gas allows the fuel gas to be individually supplied to the distributor, and the fuel and oxygen are only mixed in the reaction zone of the distributor. The combustible gas mixture is provided to the dryer. A mixture of oxygen and one or more hydrocarbons, such as decane, ethane 'acetylene, propane or another fuel, is added to the precursor mixture or separately provided to the processing chamber. Alternatively, oxygen or air may be added to the precursor mixture and the hydrocarbons provided through separate conduits. The gas mixture can be reacted to provide thermal energy for the formation of nanocrystals. The thermal energy evaporates any residual liquid in the reaction mixture and recrystallizes the electrochemical precursor to form a stream of nanocrystals that exit the processing chamber and move toward the substrate. Excess carbon can be added to the reaction mixture to promote the formation of a carbonaceous coating on the nanocrystals. Excessive carbon in the nanocrystals ~ condensed around the nanocrystals in wartime 'and provides thermal insulation to form a flattening touch. ... Cards corpus callosum to avoid the formation of the nano-body any unwanted thermal effects. The energy input is controlled by the amount of excess carbon in the reaction mixture to control the energy input to the electrified wind & the precursor and/or chamber temperature 20 201112466 degrees. The specific heat of excess carbon absorbs a portion of the thermal energy from the combustion mixture, while the thicker carbon coating on the nano-HB body reduces heat input to the nanocrystals. In addition, the carbon deposition in the final film improves the electrical properties of the film and promotes the attachment of nanocrystals to the substrate. The hydrogen-containing carrier gas can also be used to control the temperature in the chamber due to the reaction of hydrogen with the oxygen in the reaction mixture. The temperature in the processing chamber is typically maintained between about 6 〇〇〇c and about 15 〇 (rc, for example between about 8 ° C and about i, 20 (rc, for example about 1 〇〇〇 ec. Precursor The mixture comprises an electrochemically active material of the formula LiNiwMgxC〇y〇z wherein w, X and ruthenium are each between about 0.3 and 1.5 and the z-line is between about 1.5 and 2.5. The nanocrystals are comprised of a hot gas. Streaming out of the processing chamber to the embodiment, the nanocrystal exits the processing chamber at a rate of between about 100 mm/sec and about 600 mm/sec (e.g., about 3 mm/sec). A jet between about 丨. and i 5 m (e.g., about i(7)). The substrate is typically disposed between the process chambers about 〇丨 and 丨5. The conjugate is injected into the stream exiting the processing chamber. The material is typically a polymer that promotes the attachment of nanocrystals to the substrate, and the conjugate may, in certain embodiments, also provide some desired electrical properties, typically in the form of a liquid such as a solution, suspension or emulsion. An conjugate is provided. In one embodiment, the conjugate is a denatured styrene-butadiene rubber material in an aqueous emulsion. The conjugate precursor The flow rate is usually between about 10% and 3375% of the electrochemical precursor flow rate of Room 15 in the King's, for example, about 3 (%). The conjugate and the nanocrystal are mixed at a position selected for the energy content thereof. The residual heat in the nanocrystal stream evaporates the continuous phase of the solvent or liquid, allowing the conjugate to freely contact the nanocrystal. The processing chamber exit and the substrate together define the nanometer 21 201112466 Crystal spray distance, at the junction The chamber exit σ and the joint m point are bounded by the nanocrystal: distance. In most instances, the conjugate injection distance is between about 〇% and about 〇% of the coating distance of about 8%, for example Approximately 7 % of the group of precursors may be any of the electrochemically active species described herein or a. In most instances, the electrochemically active precursor comprises lithium, I: including nickel, magnesium, cobalt or the like Mixture. Different layers of lithium before the electrochemistry have different characteristics of the layer. The high-capacity layer can be formed by depositing nickel-rich mica. Using the above formula, if the W system is large; The layer will be a high-capacity layer. If χ and y are each higher than about, then the layer will be It is a high stability layer. In some embodiments, the composite layer can be deposited by changing the composition of the electrochemical precursor during deposition. By providing different precursors at different points in the process, high formation can be achieved. A composite layer of a core of capacity and a layer of high stability. While the above is directed to embodiments of the invention, other and further embodiments of the invention may be devised without departing from the basics of the invention. BRIEF DESCRIPTION OF THE DRAWINGS For a more detailed understanding of the above described features of the invention, reference should be The exemplary embodiments are not to be considered as limiting the scope of the invention, as the invention may 22 201112466 FIG. 1 is a schematic diagram of a Li-ion battery according to an embodiment. Figure 2 is a flow chart summarizing a method in accordance with an embodiment. Figure 3 is a schematic cross-sectional view of a film forming apparatus according to an embodiment. Fig. 4 is a schematic cross-sectional view showing a film forming apparatus according to another embodiment. Fig. 5 is a schematic cross-sectional view of a film forming apparatus according to another embodiment. Fig. 5 is a schematic side view of a film forming apparatus according to another embodiment. Figure 5C is an enlarged view of the apparatus of Figure 5. Figure 5D is a schematic plan view of an apparatus according to another embodiment. In order to facilitate understanding, the same component symbols are used as much as possible to indicate the same components in the drawings. It is contemplated that the elements and features disclosed in one embodiment may be used in other embodiments without particular detail. [Main component symbol description] 100 L i -ion battery 101 Load 102 Anode structure 103 Cathode structure 104 Separation layer 110 First electrolyte-containing material 111 ' 113 Current collector 112 Second electrolyte-containing material 200 Method 202 '204 ' 206 ' 208 210 Step 23 201112466 300 '402 Processing Chamber 302 Enclosure 304' 404, 502 Substrate Support 306, 406, 504, 577A, 577B Dispenser 308 '408 First Chamber 310, 314 '508 Internal 3 12 Second Chamber 3 16 first access port 318 second access port 320 ' 532 ' 534 > 536 324 ' 522 , 562 first opening 326 ' 526 , 564 second opening 328 nano crystal flow 334 , 426 ignition source 336 , 434 Flow controller 338 first source conduit 400 ' 500 ' 540 ' 595 device 412 first port 414 second conduit 418 opening 420 ' 524 nozzle 422 mixing region 424 third conduit 428 particulate trap 430 exhaust outlet 432 processing region 436 first Pipe 444 Actuator 506 Activation Chamber 512 Gas Chamber 518 Port 528 Mixing Zone 530 Spray Pattern 550, 584 Conveyor 560 Roller 570 Warm-up Depositing a layer 575 of the substrate 580 585A '5 85B conduit retainer 590 Controller 24